Patent GB-1284965-A (GB)
Title: Epoxy compounds and a process for the manufacture thereof
IPC: C07D303/46
Filed: 1970-08-20
Abstract: 1284965 Epoxy compounds F HOFFMANNLA ROCHE & CO AG 20 Aug 1970 [29 Aug 1969] 40072/70 Heading C2C The invention comprises epoxy compounds of formula wherein n is 0 or 1; A and B individually denote hydrogen or together denote a carbon-carbon bond; R signifies C 1-6  alkyl; R 3  signifies -CH 3  or -C 2 H 5 , and Y represents a group of formula -CN, -COOR 1  or -CH 2 OR 2  in which R 1  signifies H, C 1-6  alkyl, phenyl or phenyl substituted by C 1-6  alkyl, -OH, C 1-6  alkoxy or halogen and R 2  signifies H, C 1-6  alkyl, C 1-6  alkanoyl, C 6-12  aroyl, amino-(C 1-6  alkyl) (which may be mono- or di-substituted by C 1-6  alkyl), phenyl or phenyl substituted by C 1-6  alkyl, C 1-6  alkoxy, methylenedioxy or halogen. These compounds may be obtained by reacting a compound of formula in which R, R 3 , A, B and n are as above, with a phosphine oxide of formula in which R 6  denotes -CN or -COOR<SP>1</SP> 1  wherein R<SP>1</SP> 1  represents C 1-6  alkyl, phenyl or phenyl substituted by C 1-6  alkyl, C 1-6  alkoxy or halogen and R 4  and R 5  represent alkoxy or phenoxy which may be substituted by alkoxy, nitro or halogen; or reacting a compound of formula wherein R, R 3 , A, B and n are same as above and X signifies halogen, with a compound of formula MOR<SP>1</SP> 2  wherein R<SP>1</SP> 2  signifies C 1-6  alkyl, C 1-6  alkanoyl, C 6-12  aroyl, amino-(C 1-6  alkyl) which may be mono- or di-substituted by C 1-6  alkyl, phenyl or phenyl substituted by C 1-6  alkyl, C 1-6  alkoxy, methylenedioxy or halogen and M signifies an alkali or alkaline earth metal; or epoxidizing a compound of formula in which R, R 3 , A, B, Y and n have the significance given earlier, C denotes hydroxy and D denotes Cl, Br, or I, or D denotes -OH and C denotes Cl, Br or I or C and D together denote a carbon-carbon bond, or etherifying or esterifying a compound of Formula VI wherein Y denotes -CH 2 OH and C and D together denote an oxygen bridge and, if desired, saponifying an ester of Formula I obtained. 10,11 - Epoxy- 3,7,10,11 - tetramethyl - 2,6 - dodecadienoic acid ethyl ester is prepared by reacting 9,10-epoxy- 6,9,10 - trimethyl - undec - 5 - en - 2 - one (A) with diethylphosphonoacetic acid ethyl ester in Example 1. The intermediate A is obtained by epoxidizing 6,9,10-trimethyl-undeca-5,9-dien-2- one. In Example 2, 10,11-epoxy-3,7,10,11 tetramethyl-2,6-dodecadienoic acid ethyl ester is prepared by the epoxidation of 3,7,10,11- tetramethyl - 2,6,10 - dodecatrienoic acid ethyl ester (B). The intermediate (B) is obtained by treating 6,9,10-trimethyl-5,9-undecadien-2-one with diethylphosphonoacetic acid ethyl ester. In Example 3 there is prepared 10,11-epoxy. 3,7,10,11 - tetramethyl - 2,6 - dodecadienoic acid phenyl ester by epoxidizing 3,7,10,11- tetramethyl - 2,6,10 - dodecatrienoic acid phenyl ester (C). The intermediate (C) is prepared by hydrolysing the intermediate ester (B) to form 3,7,10,11 - tetramethyl - 2,6,10 - dodecatrienoic acid, and subsequently treating the acid with phenol to obtain the phenyl ester. In Example 4 there is prepared 10,11-epoxy-1-ethoxy 3,7,10,11 - tetramethyl - 2,6 - dodecadiene by the reaction of 10,11-epoxy-3,7,10,11-tetramethyl - 2,6 - dodecadien - 1 - ol (D) with ethyliodide. The intermediate (D) is obtained by the following steps: (a) preparation of 1-acetoxy- 3,7,10,11 - tetramethyl - 2,6,10 - dodecatriene by the reaction of 1 -bromo-3,7,10,11 -tetramethyl- 2,6,10-dodecatriene with Ca(OOCCH 3 ) 2 ; (b) treatment of the product of step (a) with N- bromosuccinarnide to obtain 1-acetoxy-10-bromo- (or hydroxy)-11-hydroxy- (or bromo)-3,7,10,11- tetramethyl-2,6-dodecadiene; and (c) epoxidizing and hydrolysing the product of step (b) to obtain 10,11 - epoxy - 3,7,10,11 - tetramethyl - 2,6- dodecadien-1-ol. Alternatively the intermediate D is obtained by hydrolysing 1-acetoxy- 3,7,10,11 - tetramethyl - 2,6,10 - dodecatriene (prepared in step (a)) to obtain 3,7,10,11- tetramethyl - 2,6,10 - dodecatriene - 1 - ol. This compound may also be obtained by the hydrolysis of 3,7,10,11-tetramethyl-2,6,10-dodecatrienoic acid ethyl ester, and epoxidizing the resulting alcohol. In Example 5 there is prepared 10,11- epoxy - 1 - methoxy - 3,7,10,11 - tetramethyl- 2,6-dodecadiene by the epoxidation of 1-methoxy - 3,7,10,11 - tetramethyl - 2,6,10 - dodecatriene (E). The intermediate (E) is obtained by the following steps:-(a) reaction of acetylene with 6,9,10 - trimethyl - 5,9 - undecadien - 2- one to form 3,7,10,11-tetramethyl-6,10-dodecadien-1-yn-3-ol; (b) reduction of the alcohol obtained in step (a) to produce 3,7,10,11-tetramethyl - 1,6,10 - dodecatrien - 3 - ol; (c) bromination of the product of step (b) to produce 1 - bromo - 3,7,10,11 - tetramethyl - 2,6,10 - dodecatriene; and (d), converting the bromo derivative into 1-methoxy derivative by treatment with Na/C 2 H 5 OH. In Example 6 there is prepared 6,7 - epoxy - 3,6,7 - trimethyl - 1 - [3,4- (methylenedioxy) - phenoxy] - 2 - octene by the epoxidation of 3,6,7 - trimethyl - 1 - [3,4- (methylenedioxy) - phenoxy] - 2,6 - octadiene (F). The intermediate F is obtained by the reaction of 1 - bromo - 3,6,7 - trimethyl - 2,6 - octadiene with 3,4-methylenedioxy-phenol. In Examples 7-9 the following compounds are prepared:- 10,11 - epoxy - 3,7,10,11 - tetramethyl - 2,6- dodecadiene nitrile and 10,11-epoxy-3,7,10,11- tetramethyl-(2-diethylamino-ethyl) ether. The compounds of the invention are reported to have pesticidal properties.